Chapter 1.

INTRODUCTION AND PRINCIPLES

This chapter introduces some of the basic principles of quantum mechanics. First, it reviews the
experimental results that overthrew the concepts of classical physics. These experiments led to the
conclusion that particles may not have an arbitrary energy and that the classical concepts of ‘particle’
and ‘wave’ blend together. The overthrow of classical mechanics inspired the formulation of a new set
of concepts and led to the formulation of quantum mechanics. In quantum mechanics, all the properties
of a system are expressed in terms of a wavefunction that is obtained by solving the Schrödinger
equation. We see how to interpret wavefunctions. Finally, we introduce some of the techniques of
quantum mechanics in terms of operators, and see that they lead to the uncertainty principle, one of the
most profound departures from classical mechanics.

1.1. THE ORIGINS OF QUANTUM MECHANICS

It was once thought that the motion of atoms and subatomic particles could be expressed
using classical mechanics, the laws of motion introduced in the seventeenth century by Isaac
Newton, for these laws were very successful at explaining the motion of everyday objects and
planets. However, towards the end of the nineteenth century, experimental evidence
accumulated showing that classical mechanics failed when it was applied to particles as small
as electrons, and it took until the 1920s to discover the appropriate concepts and equations for
describing them. We describe the concepts of this new mechanics, which is called quantum
mechanics.
In brief, the basic principles of classical mechanics show that classical physics (1)
predicts a precise trajectory for particles, with precisely specified locations and momenta at
each instant, and (2) allows the translational, rotational, and vibrational modes of motion to be
excited to any energy simply by controlling the forces that are applied . These conclusions
agree with everyday experience. Everyday experience, however, does not extend to individual
atoms, and careful experiments of the type described below have shown that classical
mechanics fails when applied to the transfers of very small energies and to objects of very
small mass.
We shall investigate the properties of light. In classical physics, light is described as
electromagnetic radiation, which is understood in terms of the electromagnetic field, an
oscillating electric and magnetic disturbance, that spreads as a harmonic wave, wave
displacements that can be expressed as sine or cosine functions, through empty space, the
vacuum. The wave travels at a constant speed called the speed of light, c, which is about 3×108
m s−1. As its name suggests, an electromagnetic field has two components, an electric field that
acts on charged particles (whether stationary of moving) and a magnetic field that acts only on
moving charged particles. The electromagnetic field is characterized by a wavelength, λ
(lambda), the distance between the neighbouring peaks of the wave, and its frequency, ν (nu),
the number of times per second at which its displacement at a fixed point returns to its original
value (Fig. 1.1). The frequency is measured in hertz, where 1 Hz = 1 s−1. The wavelength and
frequency of an electromagnetic wave are related by
 = c (1.1)
Therefore, the shorter the wavelength, the higher the frequency. The characteristics of
the wave are also reported by giving the wavenumber,  (nu tilde), of the radiation, where

(1.2)
1
Wavenumbers are normally reported in reciprocal centimetres (cm−1).

Fig. 1.1 The wavelength, λ, of a wave is the peak-to-peak distance. (b) The wave is shown travelling to
the right at a speed c. At a given location, the instantaneous amplitude of the wave changes through a
complete cycle (the five dots show half a cycle). The frequency, ν, is the number of cycles per second
that occur at a given point.

Figure 1.2 summarizes the electromagnetic spectrum, the description and classification
of the electromagnetic field according to its frequency and wavelength. ‘Light’ is
electromagnetic radiation that falls in the visible region of the spectrum. White light is a
mixture of electromagnetic radiation with wavelengths ranging from about 400 nm to about
700 nm (1 nm = 10−9 m). Our eyes perceive different wavelengths of radiation in this range as
different colours, so it can be said that white light is a mixture of light of all different colours.

Fig. 1.2 The electromagnetic spectrum and the classification of the spectral regions.

1.1.1. Energy quantization

The overthrow of classical mechanics and its replacement by quantum mechanics was
driven, as always in science, by noticing that experimental observations conflicted with the
predictions of accepted theory. Here we outline two examples of experiment overthrowing
current theory, which came to light at the end of the nineteenth century and which drove
scientists to the view that energy can be transferred only in discrete amounts.
In 1900, the German physicist Max Planck found that he could account for the
experimental observations by proposing that the energy of each electromagnetic oscillator is
limited to discrete values and cannot be varied arbitrarily. This proposal is contrary to the
viewpoint of classical physics in which all possible energies are allowed and every oscillator
has a mean energy kT. The limitation of energies to discrete values is called the quantization
of energy. In particular, Planck found that he could account for the observed distribution of
energy if he supposed that the permitted energies of an electromagnetic oscillator of frequency
ν are integer multiples of hν:
2
 (1.3)
where h is a fundamental constant now known as Planck’s constant. The currently accepted
value for h is 6.626 × 10−34 J s.
The most compelling and direct evidence for the quantization of energy comes from
spectroscopy, the detection and analysis of the electromagnetic radiation absorbed, emitted, or
scattered by a substance. The record of light intensity transmitted or scattered by a molecule as
a function of frequency (ν), wavelength (λ), or wavenumber ( = ν/c) is called its spectrum
(from the Latin word for appearance).
1.1.2. Wave–particle duality
At this stage we have established that the energies of the electromagnetic field and of
oscillating atoms are quantized. In this section we shall see the experimental evidence that led
to the revision of two other basic concepts concerning natural phenomena. One experiment
shows that electromagnetic radiation—which classical physics treats as wave-like—actually
also displays the characteristics of particles. Another experiment shows that electrons—which
classical physics treats as particles—also display the characteristics of waves.
(a) The particle character of electromagnetic radiation
The observation that electromagnetic radiation of frequency ν can possess only the
energies 0, hν, 2hν, . . . suggests (and at this stage it is only a suggestion) that it can be thought
of as consisting of 0, 1, 2, . . . particles, each particle having an energy hν. Then, if one of these
particles is present, the energy is hν, if two are present the energy is 2hν, and so on. These
particles of electromagnetic radiation are now called photons. The observation of discrete
spectra from atoms and molecules can be pictured as the atom or molecule generating a photon
of energy hν when it discards an energy of magnitude ΔE, with ΔE = hν.
(b) The wave character of particles
Although contrary to the long-established wave theory of light, the view that light
consists of particles had been held before, but discarded. No significant scientist, however, had
taken the view that matter is wave-like. Nevertheless, experiments carried out in 1925 forced
people to consider that possibility. The crucial experiment was performed by the American
physicists Clinton Davisson and Lester Germer, who observed the diffraction of electrons by a
crystal. Diffraction is the interference caused by an object in the path of waves. Depending on
whether the interference is constructive or destructive, the result is a region of enhanced or
diminished intensity of the wave. The Davisson–Germer experiment, which has since been
repeated with other particles (including α particles and molecular hydrogen), shows clearly that
particles have wave-like properties.
We have also seen that waves of electromagnetic radiation have particle-like properties.
Thus we are brought to the heart of modern physics. When examined on an atomic scale, the
classical concepts of particle and wave melt together, particles taking on the characteristics of
waves, and waves the characteristics of particles.
Some progress towards coordinating these properties had already been made by the
French physicist Louis de Broglie when, in 1924, he suggested that any particle, not only
photons, travelling with a linear momentum p =mv (with m the mass and v the speed of the
particle) should have in some sense a wavelength given by the de Broglie relation:

(1.4)

3
 That is, a particle with a high linear momentum has a short wavelength (Fig. 1.3).
Macroscopic bodies have such high momenta (because their mass is so great), even when they
are moving slowly, that their wavelengths are undetectably small, and the wave-like properties
cannot be observed. This undetectability is why, in spite of its deficiencies, classical mechanics
can be used to explain the behaviour of macroscopic bodies. It is necessary to invoke quantum
mechanics only for microscopic systems, such as atoms and molecules, in which masses are
small.

Fig. 1.3 An illustration of the de Broglie relation between momentum and wavelength. The
wave is associated with a particle (shortly this wave will be seen to be the wavefunction of the
particle). A particle with high momentum has a wavefunction with a short wavelength, and vice
versa.
We now have to conclude that, not only has electromagnetic radiation the character
classically ascribed to particles, but electrons (and all other particles) have the characteristics
classically ascribed to waves. This joint particle and wave character of matter and radiation is
called wave–particle duality. Duality strikes at the heart of classical physics, where particles
and waves are treated as entirely distinct entities. We have also seen that the energies of
electromagnetic radiation and of matter cannot be varied continuously, and that for small
objects the discreteness of energy is highly significant. In classical mechanics, in contrast,
energies could be varied continuously. Such total failure of classical physics for small objects
implied that its basic concepts were false. A new mechanics had to be devised to take its place.